Novel organotin compounds

ABSTRACT

1. A COMPOUND OF THE FORMULA   R-S(=O)-CH2-SN-R&#39;&#39;3   WHERE R IS C1 TO C14 ALKYL, ARYL OR SUBSTITUTED ARYL WHEREIN THE ARYL SUBSTITUENTS ARE SELECTED FROM THE GROUP CONSISTING OF C1 TO C4 ALKYL, C1 TO C4 ALKOXY, HALOGEN AND NITRO, AND R&#39;&#39; IS C1 TO C10 ALKYL.

United States Patent O 3,850,970 NOVEL ORGANOTIN COMPOUNDS Donald J.Peterson, Cincinnati, and James F. Ward, Fairfield, Ohio, assignors toThe Procter & Gamble Company, Cincinnati, Ohio No Drawing. Filed Mar. 8,1973, Ser. No. 339,449 Int. Cl. C07t 7/22 US. Cl. 260-429.7 12 ClaimsAIBSTRACT OF THE DISCLOSURE Disclosed are novel (organosulfinylmethyl)triorganotin compounds and a process for preparing same. These organotincompounds correspond to the general formula:

R-g-CH2SI1R'3 where R is a 1 to 14 carbon atom alkyl, aryl orsubstituted aryl group and each R is an alkyl group of 1 to carbonatoms. The organotin compounds of the invention have insecticidal,acaricidal and herbicidal properties and are employed in the formulationof pesticidal compositions effective for combating these pests.

BACKGROUND OF" THE INVENTION This invention relates to novel compounds.More particularly, this invention relates to novel(organosulfinylmethyl) triorganotin compounds, a method for theirpreparatiou, pesticidal compositions containing such compounds and to amethod of combating pests.

The desirability of controlling or eradicating various insects and weedsis clearly accepted. Thus, compounds possessing insecticidal,acaricidal, and herbicidal properties and especially adapted to suchcontrol or eradication are of particular importance.

It is an object of the present invention to provide novel organotincompounds and a method for their preparation.

A further object is to provide novel compounds which are useful aspesticides. Another object is to provide pesticidal compositionscontaining the novel organotin compounds. A still further object is toprovide novel compositions and methods effective for combating pests.Other objects of the invention will be apparent from consideration ofthe invention described more fully hereinafter.

DETAILED DESCRIPTION OF THE INVENTION The novel (organosulfinylmethyl)triorganotin compounds of the present invention have the formula:

where R is a member selected from the group consisting of a 1 to 14carbon atom alkyl, aryl and substituted aryl radicals wherein in thesubstituted aryl radicals the sub stituents are selected from the groupconsisting of C to C alkyl, C -C alkoxy, halogen, and nitro, and whereinR is alkyl containing from 1 to about 10 carbon atoms. Preferably R ismethyl or phenyl and R is O; to C straight chain alkyl. When R is C; toC alkyl, the compounds have been found to be optimum with respect tohigh pesticidal activity and low mammalian toxicity. EX- arnples ofcompounds of the invention are:

(methylsulfinylmethyl) triethyltin, (methylsulfinylrnethyl)tri-n-butyltin, (methylsulfinylmethyl) tri-n-hexyltin,(n-hexylsulfinylmethyl) tri-n-hexyltin, (n-dodecylsulfinylmethyl)tri-n-butyltin, (2-naphthylsulfinylmethyl) tri-n-butyltin,

(phenylsulfinylmethyl) tri-n-butyltin, (4-ch1orophenylsulfinylmethyl)tri-isopropyltin, (4-bromo-2-naphthylsulfinylmethyl) tri-n-butyltin,(4-methyl-2-naphthylsulfinylrnethyl) tri-n-hexyltin,(4-nitrophenylsulfinylmethyl) tri-n-butyltin, and(2-ethoxyphenylsulfinylrnethyl) tri-n-butyltin.

The R groups on the tin can also be mixed as for example in(methylsulfinylmethyl) methyl diethyltin. Preferred compounds are(methylsulfinylmethyl) tri-n-butyltin, (methylsulfinylmethyl)tri-n-hexyltin, (phenylsulfinylmethyl) tri-n-butyltin and(phenylsulfinylmethyl) tri-nhexyltin.

In its process aspect, the invention provides a method of preparing thenovel (organosuifinylmethyl) triorganotin compounds, comprising thesteps of:

(1) Admixing a triorganotin amine compound of the formula (R' Sn) NR"wherein x is an integer from 1 to 3 and where R is as defined above andR" is as defined hereinafter, with a methyl sulfoxide of the formulaRS(O)CH wherein R is as defined above, and

(2) Heating the mixture from Step (1) at a temperature of from about 25C. to C., and recovering the (organosulfinylmethyl) triorganotincompound.

The reaction can be described graphically as follows:

heat (R'aSl1)xNR XRS(O)OH3 XRS(O)CH2S11R3 R'qh NH: wherein x is aninteger from 1 to 3, wherein R and R are defined as above and wherein R"is C -C alkyl, cycloalkyl, or hydrogen.

The organotin amines used as reactants in the above reaction can beprepared by reacting the alkali metal salts of ammonia and primary andsecondary amines with triorganotin halides, e.g. triorganotin fluorides,chlorides, bromides and iodides, which are commercially available. Thealkali metal salts of primary and secondary amines and ammonia arethemselves prepared by reacting said amines or ammonia With thecorresponding metals in the manner well-known to those skilled in theart. For example, ammonia will react with sodium to yield sodamide,which, in turn will react with a triorganotin halide to prepare thecorresponding triorganotin amine. Dimethylamine will react with lithiummetal in the presence of a conjugated diene such as butadiene to formlithium dimethylamide, which, in turn, reacts with a triorganotin halideto form the (N,N-dimethylamino) triorganotin compound. Alternatively,various amines can be metalated in standard fashion with, for example,organolithium compounds to provide the metal amides. In general terms,the preparation of the triorganotin amines useful herein is representedby the following reaction sequence:

where M is alkali metal, i.e. lithium, sodium, potassium, rubidium andcesium; wherein R and R are as defined above and X is halide, i.e.fluoride, chloride, bromide or iodide. It will be recognized that whenprimary amines and ammonia are used, varying ratios of triorganotinamines of the formula (R Sn) NR and R SnHNR", and (R Sn) N, (R Sn) NHand R SnNH respectively, are formed. These are all useful in preparingthe (organosulfinylmethyDtriorganotin compounds of the presentinvention.

For economic reasons, sodium is the preferred alkali metal for use inpreparing the alkali metal salts of the amines. Ammonia or any aminehaving at least one N-H bond capable of recting with a metalating agentto form an alkali metal amine salt is suitable for preparing thetriorganotin amines used herein. Generally, however, ammonia and alkylamines containing from 1 to 6 carbon atoms, and preferably 1 to 4 carbonatoms, are preferred. Exemplary amines used in this procedure includemethylamine, dimethylamine, ethylamine, diethylamine and ammonia.Especially preferred herein are ammonia, methylamine, dimethylamine,ethylamine and diethylamine. This is for economic reasons and alsobecause these amines, when liberated during the reaction between thetriorganotin amine and the sulfoxide, are easily removed by distillationfrom the reaction medium due to their relatively high volatility. Thetriorganotin halides suitable for preparing the triorganotin amines usedherein are commercially available. Such compounds are prepared, forexample, by reacting an organometallic compound with a tin tetrahalidein the manner well-known to those skilled in the art. Exemplarytriorganotin halides suitable for preparing the triorganotin amines usedin the present process include trimethyltin chloride, triethyltinbromide, tripropyltin fluoride, tributyltin chloride, tris-decyltinchloride and the like. The trialkyl tin chlorides are preferred foreconomic reasons.

From the foregoing it may be seen that a variety of trialkyltin aminesuseful in the present process can be readily prepared using standardtechniques. To facilitate ease of removal of the liberated amine in thereaction of the trialkyl tin amine with the sulfoxide it is generallypreferred that the R" groups on the trialkyltin amine be hydrogen,methyl or ethyl. Preferred trialkyltin amines used in the process of thepresent invention are the bis (trialkyltin) amines [(R Sn) NH],tris(trialkyltin) amines [(R Sn) N], bis(trialkyltin)-N-methylaminesaminotrialkyltins [R' SnNHz], N-methylaminotrialkyltins [R SnNHCH andN,N-dimethylaminotrialkyltins [R' SnN(CH Of these, the compounds whereinR is straight chain C to C alkyl are preferred. When ease of preparationand handling are of primary concern, N,N- diethyl C C straight chainalkyl tin or N,N-dimethyl C -C straight chain alkyl tin are preferablyused.

The methyl sulfoxides used in the process herein have the formulaRS(O)CH wherein R is C to C alkyl, aryl or substituted aryl wherein thearyl substituents are selected from the group consisting of halogen,nitro, C to C alkyl and C to C alkoxy. Such methyl sulfoxides arecommercially available or, alternatively they can be prepared inwell-known fashion by the controlled oxidation of the correspondingsulfides of the formula RSCH using, for example, hydrogen peroxide inglacial acetic acid, sodium hypochlorite, or potassium permanganate atelevated temperatures, as oxidizing agents. Examples of sulfoxides foruse in the present process are: dimethyl sulfoxide, n butyl methylsulfoxide, n-octyl methyl sulfoxide, phenyl methyl sulfoxide, Z-naphthylmethyl sulfoxide, 4-chlorophenyl methyl sulfoxide, 4-bromo-2-naphthylmethyl sulfoxide, 4-nitrophenyl methyl sulfoxide, 4- ethylphenyl methylsulfoxide, 3-methoxyphenyl methyl sulfoxide and 4-ethoxyphenyl methylsulfoxide. Especially preferred are dimethyl sufoxide and phenyl methylsulf oxide.

The process herein is generally carried out by admixing the triorganotinamine with the sulfoxide at a molar equivalent ratio of from about 1:100to 100:1, preferably, about 1:1; conducting the reaction at atemperature fiom about 25 C. to 125 C. for a period from about 1 toabout 24 hours; and recovering the desired (organosulfinylmethyl)triorganotin compound by crystallization, chromatography ordistillation, depending on the physical form of the compound beingprepared. For example, liquid (organosulfinylmethyl) triorganotincompounds are generally recovered by distillation while the solid(organosulfinylmethyl) triorganotin compounds are readily recovered bycolumn chromatography or crystallization. Preferably, in order toimprove the degree of reaction completion, the free amine which isformed during the reaction is continuously removed by distillation.

While the process of this invention is preferably carried out in theabsence of solvent, it is sometimes convenient to use a solvent orsuspending liquid herein. Any of the common organic solvents can be usedfor this purpose, including for example, hexane, benzene, toluene,xylene, and the like. Mixtures such as the petroleum ethers and theglyme solvents are also suitable. If a solvent is used, its boilingpoint should preferably exceed that of the liberated amine so that theamine can be continuously removed by distillation. Preferred solventsare anhydrous aprotic organic liquids, expecially xylene. Sufiicientsolvent is used to dissolve or disperse the reactants.

The reaction temperature in this process should be at least 25 C. toensure a reasonable reaction rate, but should not exceed 125 C. sinceside reactions and decomposition of the principal reaction product tendto occur at temperatures above about 125 'C. Preferably, the reactiontemperature should be from about 50 to 100 C. The reaction is initiatedalmost immediately upon mixing, and the reaction time employed will varywith temperature, the amount of tin amine being reacted with thesulfoxide, and the like. Usually, from about 10 minutes to 24 hours issufficient.

The novel compounds of the present invention are useful for destroying avariety of pests, particularly insects, mites and weeds. Accordingly, amethod aspect of the present invention comprises combatting pests byapplying to said pests or their habitat a pesticidally effective amountof one or more of the novel compounds of the invention. The requireddosage depends upon many factors such as method of application, type anddegree of pest infestation, frequency of treatment, climatic conditions,etc. In agricultural use (i.e. on field crops) application rates ofabout 0.5 to 50 lbs. of organotin compound per acre are usuallysatisfactory, but higher rates can also be used. Preferably theapplication rate is about 1 to 30 lbs. per acre.

For practical use as pesticides, the organotin compounds of theinvention are generally incorporated into pesticidal compositions whichcomprise an inert carrier and a pesticidally effective amount of one ormore of the organotin compounds. (As used herein an inert carrier isdefined as a solvent or a dry bulking agent which has substantially nopesticidal effectiveness but which provides a means whereby theorganotin compounds are diluted for convenient application.) Suchcompositions enable the organotin compounds to be applied convenientlyto pests or their habitats in any desired quantity. These compositionscan be solids, such as dusts, granules or wettable powders, or they canbe liquids such as solutions, aerosols, or emulsifiable concentrates.The solid compositions generally contain from about 0.5% to about byweight of the organotin compounds and the liquid compositions generallycontain from about 0.5 to about 70% by weight of said compounds.

Dusts can be prepared by grinding and blending the organotin compoundswith a solid inert carried such as talcs, clays, silicas, pyrophyliteand the like. Granular formulations can be prepared by impregnating theorganotin compounds, usually dissolved in a suitable solvent, onto andinto granulated carriers such as the attapulgites or the ver miculites,usually of a particle size range of from about 0.3 to 1.5 mm., or bycoating an inert carrier with a wettable powder formulation of thecompounds. Wettable powders, which can be dispersed in water or oil toany desired concentration of the organotin compounds, can be prepared byincorporating wetting agents into concentrated dust compositions.

Preferred pesticidal compositions for the practice of the inventionherein are emulsifiable concentrates which comprise the organotincompound, and, as an inert carrier, an emulsifier and an organicsolvent. Such concentrates can be extended with water and/or additionalorganic solvent to any desired concentration of the organo- 3,850,970 6tin compound for application as sprays to the site of pest EXAMPLE IIinfestation. The emulsifiers used in these concentrates are surfaceactive agents of the anionic, nonionic, cationic, Preparatlon of(methylsulfinylmethyl) mbutyltm ampholytic or zwitterionic type andnormally comprise Dimethylamino tributyltin (33.4 g.; 0.1 moles) anddifrom about 0.1% to 30% by weight of the Concentrate. methylsulfoxide(100 g.; 1.28 moles) were stirred in a Examples of suitable an ionicsurface active agents are 250 ml. reaction flask, under a positivepressure argon sodium salts of fatty alcohol sulfates having from 8-18atmosphere, for 4.5 hours at 80 C. During the reaction, carbon atoms inthe fatty chain and sodium salts of alkyl liberated dimethylamine gasexited from the reaction benzene sulfonates, having from 9 to 15 carbonatoms flask through an open port with the moving argon gas. in the alkylchain. Examples of suitable nonionic surface 10 The reaction stoodovernight at ambient temperature. active agents are the polyethyleneoxide condensates of Excess dimethylsulfoxide was distilled at 75 C. atalkyl phenols, wherein the alkyl chain contains from about mm. Hg. Thereaction product was distilled through a 6 to 12 carbon atoms and theamount of ethylene oxide semi-micro distillation apparatus at 138 C. at0.1 mm.

condensed onto each mole of alkyl phenol is from about 5 Hg. Yield of 25g. (68%) was identified as (methylsulto 25 moles. Examples of suitablecationic surface active 15 finylmethyl) tributyltin by 'H NMR andinfrared spectra.

agents are dimethyl dialkyl quaternary ammonium salts wherein the alkylchains contain from about 8 to 18 EXAMPLE HI carbon atoms and the saltforming anion is a halogen. Compounds of the invention were tested forherbicidal Examples of suitable ampholytic surface active agentseffectiveness according to the following procedure. are derivatives ofaliphatic secondary or tertiary amines 20 (a) Preparation andapplication of materials: in which one of the aliphatic substituentscontains from The desired amount of compound was dissolved in about 8 to18 carbon atoms and one contains an anionic acetone, containing 500p.p.m. of Span 85 (sorbitan triwater solubilizing group, e.g. sulfate orsulfo. Specific at mu and Tween 89 (p y y y suitable ampholytic surfaceactive agents are sodium-3- bitan monooleate emulsifier). Theformulations are apdodeeylaminopropionate andsodium-3-dodecylaminoproplied with a Devilbiss atomizer operating at 6p.s.i. prespane-l-sulfonate. Examples of suitable zwitterionic sursureand delivering 50 ml. of formulation on both preface active agents arederivatives of aliphatic quaternary emergence and post emergence pots.ammonium compounds in which one of the aliphatic con- (b) Pre-emergencetests: stituents contains from about 8 to 18 carbon atoms and Duplicatepaper pots filled with a soil mixture are one contains an anionic watersolubilizing group. Specific seeded at a depth of one-half inch withmustard, pigweed examples of zwitterionic surface active agents are3-(N, crabgrass and foxtail. Immediately after seeding, the soil Ndimethyl-N-hexadecylammonio) propane-l-sulfonate is sprayed with thesolution. Growth is allowed to ocand 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy cur under artificial lightwith overhead irrigation. The propane-l-sulfonate. Many other suitablesurface active plants are observed for about 10 days and an injuryratagents are described in Detergents and Emulsifiers-1972 ing is givenin comparison With untreated controls. Annual by John W. McCutcheon Inc.which is incorpo- (c) Post-emergence tests: rated by reference herein.Suitable solvents for these Duplicate paper pots filled with vermiculiteare seeded emulsifiable concentrates include hydrocarbons such as at adepth of one-half inch with the same plants embenzene, toluene, xylene,kerosene and Stoddard Solvent ployed in the pre-emergence tests. Growthoccurs under and halogenated hydrocarbons such as chlorobenzene,artificial light with irrigation provided by placing the chloroform,fiuorotrichloromethane and dichlorodifiuoroporous pots in a small amountof water in stainless steel methane. Typical liquid concentratescomprise from trays. After about 10 days, when the plants reach asuitabout 0.5% to 70% organotin compound, from about able size, they aresprayed with the formulations. Ob- 0.l% to 30% emulsifier and from about29.9% to about servations are made for 10 days and an injury rating is99.4% organic solvent. given in comparison with untreated controls.

The following examples are included herein to more Results obtained inthese tests are shown in Table 1.

TABLE 1 Mustard Pigweed Crabgrass Foxtail Treatment Pre Post Pre PostPre Post Pre Post 2 lbs/acre 5 5 4 3 "Plant injury rated on a 0 (noinjury) to 5 (death) scale.

fully illustrate the present invention but are not intended EXAMPLE IVto be limiting thereof Compounds of the invention were tested forinsecticidal effectiveness against adult house flies, southern armywormlarvae, Mexican bean beetle larvae and pea aphids in the followingmanner. The compounds are dis solved in acetone and dispersed indistilled water with emulsifiers. The emulsifiers in these aqueousdispersions were 100 ppm. Span 85 (sorbitan trioleate) and 20 p.p.m.Tween 80 (polyoxyethylene sorbitan monooleate).

o The compositions are applied for a ten-second period to pressure argonatmosphere for 20 hours at 100 Dur insects retained in a 2" 5" diameterscreened cage.

ing the reaction, liberated dimethylamine gas exited from The spray isapplied from a Waters vertical Spray towel. the macho flask through anopen P W the operating at 10 p.s.i. pressure and discharging about 30ing argon gas. The crude product was distllled through ml per minutethrough an atomizan The spray descends a sflmifflicro distillation PPThe mam fraction through an 8 inch stainless steel cylinder to theinsects g6 Y distilled at 1604700 3110-05 below the atomizer. Theinsects are retained in the Hg. The product was identified by 'H NMR andinfrared sprayed cages for mortality observations. In the case ofspectra as (phenylsulfinylmethyl) tributylin. house fly treatment, twohour data represent knockdown,

EXAMPLE I Preparation of (phenylsulfinylmethyl) tributyltin Phenylmethyl sulfoxide (7.0 g.; 0.05 moles) and dimethylamino tributyltin(16.7 g.; 0.05 moles) were admixed in a 50 ml. round bottom flask, undera positive 24-hour data refer to mortality. The results are set forth 3.The compound of claim 1 wherein the compound is in Table 2.(methylsulfinylmethyl) tri-n-hexyltin.

TABLE 2 Concen- Southern Mexican tration, Housellies armybean Pea.percent worms, beetles, aphids, Treatment w./v. 2 hr. 24 hr. 48 hrs. 48hrs. 48 hrs.

CH3S (O) CHZSX1 C4H9)3 0. 1 78 18 100 90 100 0. 05 70 60 100 0. 01 60 30C HS(O) CI-I2Sn(C4Hv)a 0. 1 8O 4 100 50 100 0. 80 100 0. 01 50 0 Thefigures indicate percent of insects killed.

EXAMPLE V Compounds of the invention were tested for miticidaleffectiveness against strawberry spider mites in the following manner.The test compositions are prepared in the same manner as in Example IV.Bean seedlings are infested with approximately one hundred mites each.The test compositions are sprayed onto the infested seedlings. After 5days the plants are examined both for post-embryonic forms of mites andfor eggs. The percentage of kill is determined on the basis of theoriginal number of mites subjected to the test treatment. The miticidalresults are reported in Table 3.

A concentrated composition of the invention is prepared by mixing thefollowing ingredients:

Percent by weight (Methylsulfinylmethyl)tri-n-butyltin Nonionicemulsifier 5 Xylene 70 *Condensation product of nonylphenol with 15moles of ethylene oxide.

The concentrate is a stable homogeneous liquid. When diluted with 100parts of water per 1 part of concentrate it forms a stable oil-in-wateremulsion which is suitable for spraying onto areas of insect and weedinfestation.

What is claimed is: 1. A compound of the formula wherein R is C to Calkyl, aryl or substituted aryl wherein the aryl substituents areselected from the group consisting of C to C alkyl, C to C alkoxy,halogen and nitro, and R is C to C alkyl.

2. The compound of claim 1 wherein the compound is(methylsulfinylmethyl) tri-n-butyltin.

4. The compound of claim 1 wherein R is aryl or substituted aryl whereinthe substituents on the aryl moiety are selected from the groupconsisting of C to C alkyl, C to C alkoxy, halogen and nitro and R is Cto C alkyl.

5. The compound of claim 4 wherein R is phenyl.

6. The compound of claim 5 wherein R is selected from the groupconsisting of C to C alkyls and mixtures thereof.

7. The compound of claim 6 wherein the compound is(phenylsulfinylmethyl) tri-n-butyltin.

8. The compound of claim 6 wherein the compound is(phenylsulfinylmethyl) tri-n-hexyltin.

9. A process of preparing novel (organosulfinylmethyl) triorganotincompounds comprising the steps of:

(l) admixing a triorganotin amine of the formula (RSn) NR with a methylsulfoxide of the formula RS(O)CH wherein R is selected from the groupconsisting of C to C alkyls, R is selected from the group consisting ofhydrogen and C to C alkyls and cycloalkyls, R is selected from the groupconsisting of C to C alkyl, aryl and substituted aryl wherein the arylsubstituents are selected from the group consisting of C to 0.; alkyl, Cto C alkoxy, halogen and nitro, and x is an integer from 1 to 3,

(2) heating the mixture of Step (1) to a temperature of from about 25 C.to 125 C., and

(3) recovering the (organosulfinylmethyl) triorganotin compound.

10. The process of claim 9 wherein R" is selected from the groupconsisting of hydrogen, methyl and ethyl.

11. The process of claim 10 wherein R is selected from the groupconsisting of C to C alkyls and mixtures thereof and R is selected fromthe group consisting of methyl and phenyl.

12. The process of claim 11, wherein the reaction is conducted at atemperature of from about C. to about C.

References Cited UNITED STATES PATENTS 3,095,434 6/1963 Stamm et al.260429.7 3,538,088 11/1970 Hartmann 260429.7 3,725,446 4/ 1973 Peterson260429.7 3,784,580 1/ 1974 Peterson 260429.7 3,794,670 2/1974 Peterson260429.7 3,808,264 4/1974 Peterson et al. 260429.7

DANIEL E. WYMAN, Primary Examiner A. P. DEMERS, Assistant Examiner US.Cl. X.R. 7l97; 424288

1. A COMPOUND OF THE FORMULA